KR20180098603A - Smile switches and electronic devices that use it - Google Patents

Abstract

A micro-switch comprising a first electrode, a second electrode and a porous polymer metal complex conductor, wherein the porous polymer metal complex conductor is represented by the following formula (1), and the metal constituting the first electrode and the second electrode Is different in oxidation-reduction potential.
[ML_x]_n(D)_y (One)
Wherein M represents a metal ion selected from Groups 2 to 13 of the Periodic Table of the Elements and L represents a ligand capable of forming two or more functional groups capable of coordinating to M and capable of crosslinking with two of M , And D represents a conductive auxiliary agent not containing a metal element. x is from 0.5 to 4, and y is from 0.0001 to 20 per x. n is [ML_x], And n is 5 or more.

Description

Smile switches and electronic devices that use it

The present invention relates to a porous polymer metal complex conductor made of a porous polymer metal complex (PCP: Porous Coordination Polymer) containing a conductive auxiliary agent, a micro switch using the same, and an electronic device using the same.

The present application claims priority based on Japanese Patent Application No. 2016-010864 and Japanese Patent Application No. 2016-010865 filed on January 22, 2016, the contents of which are incorporated herein by reference.

As used herein, the term " switch " means a mechanism for holding data by having a plurality of stable states that can be changed by any method and associating each stable state with, for example, " 0 & do. In the case of DRAM (Dynamic Random Access Memory), which is a kind of memory, there is a memory as a kind of minute switch. In the case of a flash memory, charges are injected into the floating gate Quot; 1 " and " 0 ", respectively. These microswitches are widely used as recording materials for personal computers and mobile devices, and the characteristics of the microswitches play an important role in determining the performance of devices using them.

The greatest problem of the microswitches is that the improvement of characteristics in conventional materials is approaching the limit. In order to improve the characteristics of the microswitch, a method of miniaturization has been widely adopted. This is because the smaller the size, the lower the power consumption, the higher the response speed, the more highly integrated by the high integration, and the smaller and lighter. Photolithography is generally used as the micromachining method. However, this technique also has inherent limitations as the wavelength of light, and it is known that it is difficult to reduce the size of the monolithic microswitch currently used. In addition, in the conventional method of determining the number of electrons, it is inevitable that the data is lost in accordance with the existence of the leakage path, because it is determined whether or not the charge is contained in the floating gate. It is the limit. As a method for achieving high performance, a method of laminating devices has been studied, but naturally a high technique is required for lamination, and the yield is lowered and manufacturing costs are raised.

There is a method of preventing charge leakage by using a nitride film in order to prevent the current from escaping even if the shape is made finer. However, there is a limit to miniaturization as long as the technique of photolithography due to the limit of the light wavelength described above is used.

There is also a move to develop switches with higher performance using new mechanisms, rather than refinement of existing materials. For example, as a next-generation flash memory, a magnetoresistive random access memory (MRAM), a phase change random access memory (PRAM), and a resistance random access memory (ReRAM). MRAM has a problem in that the structure is complicated, the yield is low, and the manufacturing cost is high. The PRAM performs switching using slow cooling and quenching, and the speed limit is not necessarily high in principle. Although ReRAM is not practically used at present, it is based on a mechanism for forming metal nanowires. It can be expected that stable operation can be expected by flowing a large current, that is, when it is used as a switch, And a lamination is also expected.

Porous Coordination Polymer (PCP) is a crystalline solid having nano-level pores, which is obtained from metal ions and organic ligands. From the variety of metal ions, combinations of organic ligands, and skeletal structure, , Separation materials, catalysts, sensors, medicines, and the like.

One of the characteristics of the porous polymer metal complex is its network structure. Porous polymer metal complexes of various structures such as one-dimensional chain aggregates, two-dimensional rectangular lattice laminates, and jungle gimg shape three-dimensional structures are known (Non-Patent Document 1). These porous polymeric metal complexes have a great variety of metal ions and ligands constituting the porous polymeric metal complexes in addition to the diversity of the network structure and thus can manifest various chemical properties, It is basically very difficult to estimate the physical properties to be expressed from only the ligand, and the search for materialization of the porous polymer metal complex in which various applications are conceived is performed in a state close to the hand search. (Non-Patent Document 2, Non-Patent Document 2 Literature 3).

Another characteristic of the porous polymer metal complex is the uniformity of the pore structure. The porous polymer metal complex is a crystal having a regular repeating structure formed by a metal ion and a ligand. Activated carbon is a porous material. However, among single unit particles, pores having a large and small size exist (pore diameter distribution), and the shapes of the pores are also mixed. On the other hand, since the pores of the porous polymer metal complex are composed of metal ions and ligands as described above, the pore diameter is defined by their network structure and the size of the ligand and the metal ion. Therefore, basically, As shown in Fig. Therefore, the pore diameter distribution is extremely small.

As a conventional material having porosity, zeolite can be mentioned. The zeolite, like the porous polymer metal complex, is a crystalline material and has a very small pore diameter distribution, but the pore diameter is generally larger than that of the porous polymer metal complex. In addition, since the walls of the porous polymeric metal complexes are molecules, and the wall thickness of the activated carbon or zeolite is much thicker than that of the porous polymeric metal complexes, the porous polymeric metal complexes are activated carbon Zeolite has a feature of being highly porous (high porosity) compared to zeolite. Research on the development of a gas storage separating material using a high gas separation capability expressed by a small pore diameter distribution, a small pore diameter, and a high porosity is underway.

PCP is also a material that is very easy to synthesize. A porous metal material such as zeolite or activated carbon is required to be subjected to a material firing process and requires time or energy. On the other hand, when the porous polymer metal complex is mixed with a metal ion serving as a raw material and a ligand at a temperature close to room temperature, It is known that a powder or a thin film is obtained, and in this sense, it has a good potential as an industrial material.

Since the porous polymer metal complex is synthesized from metal ions and ligands and the network structure is formed of organic molecules, the conductivity of the material itself is very low. Although the porous polymer metal complex is classified as a semiconductor, its conductivity is very low (Non-Patent Document 4).

(Japanese Patent Application Laid-Open Publication No. 2000-3558). [0004] In order to impart conductivity to a porous polymeric metal complex, application to a sensor and the like becomes possible.

There are many methods of imparting conductivity, but one of them has been studied to introduce conductivity by introducing a material for improving conductivity (hereinafter referred to as " conductive auxiliary agent ") into the pores of the porous polymeric metal complex. For example, Non-Patent Document 8 discloses a technique for improving conductivity by introducing TCNQ (tetracyanoquinodimethane) known as an organic conductor into a porous polymer metal complex film containing copper ions. According to this technique, it becomes possible to impart conductivity to the porous polymer metal complex. The porous polymer metal complex called Cu ₃ (BTC) ₂ (BTC is 1,3,5-benzenetricarboxylate), abbreviated HKUST-1, which is used in this document, has a structure in which the copper ion is in a four- It is described in this document that a conductive path is formed by forming a vacancy of the copper ion and TCNQ to form a conductive path thereby improving the conductivity. That is, it is considered that this phenomenon is established only in a specific dopant which is capable of electrostatically interacting with a copper ion having a vacant coordination site, and having a size that can be accommodated in pores and interact with copper ions. In addition, this document does not describe the use as a switch such as a memory.

Studies have also been carried out to improve the conductivity by adding TCNQ to the pores of the porous metal-metal complex containing thallium (Non-Patent Document 9). In this review, although it is possible to impart conductivity to the porous polymer metal complex, its use as a switch is not described.

Studies have been made to improve the conductivity by introducing an ionic liquid into the pores of the porous polymeric metal complex (Patent Document 1). In this review, although it is possible to impart conductivity to the porous polymer metal complex, it does not disclose whether or not a memory effect can be obtained.

A porous polymer metal complex containing TCNQ itself as a skeleton has also been developed (Non-Patent Document 10; Non-Patent Document 11; Non-Patent Document 12). Various ions have been studied, and it has been confirmed that various porous polymeric metal complexes interact with TCNQ and change in electrochemical characteristics, but it is not described whether or not a switch effect can be obtained.

As a porous polymer metal complex having a switch characteristic, Patent Document 2 and Non-Patent Document 13 are known. This material realizes the switch characteristic in the sense that the state A is transferred to the other state B and the state thereof is maintained by the addition of the gas. However, there is no description as to the change of the structure accompanying the introduction of the gas pressure, and whether or not the electrical switch characteristic can be realized.

Non-patent document 18 is known for a porous polymer metal complex into which an ammonium salt is considered to be an ionic liquid. In this document, the ammonium salt is used only as a crystallizing agent, and the influence on the physical properties such as conductivity is not disclosed.

Non-patent document 14 is known for the introduction of ammonium salts and the like to the porosity material. Although the improvement of the gas adsorption characteristics has been found by this investigation, the improvement of the conductivity and the memory effect are not disclosed.

Non-patent document 15 is known as a method for introducing a salt to a pore forming material. This review reveals improvements in conductivity and shows applications to batteries, but does not disclose memory effects.

There has been reported an electrochemical phenomenon called " resistance switching effect " in which a thin film of a porous polymer metal complex is sandwiched between electrodes, and a voltage is applied to change the resistance value (Non-Patent Document 16). According to this report, the copper ions constituting the porous polymer metal complex change to copper, and the carboxyl group of the trimesic acid, which is a ligand constituting the porous polymer metal complex, is decomposed and vaporized as a gas. As a result, an sp2 hybrid orbit is generated, whereby conductivity is generated, and it has been found that a specific effect is available as ReRAM. That is, by this method, the conductivity of the porous polymer metal complex can be improved without dopant addition, and as a result, the memory function can be manifested.

However, this method is disadvantageous in that it causes the disappearance from the skeleton of the copper ion constituting the porous polymer metal complex and precipitation into the electrode, and the skeleton of the porous polymer metal complex, which is called the carboxyl group decomposition of the ligand constituting the porous polymer metal complex With its irreversible destruction. The skeleton of the porous polymeric metal complex forms the nano-pores of the porous polymeric metal complex. The breakage of the porous polymeric metal complex is affected by the strength as a material, the change in the pore diameter, the change in the distribution of the pore diameter, And the like, as well as a variety of conductive materials. In addition, it is difficult to completely control such a material breakdown phenomenon, and as a result, the material characteristics are changed, resulting in miniaturization of the switch, miniaturization and stabilization of the operating current, and deterioration of the material over time. As described above, the technique disclosed in this document is a ReRAM that utilizes changes in the constituent material (porous polymer complex) itself, that is, dissociation and migration of the elements constituting the porous polymer complex, and inherently involves destruction of the material , The drawback is inherently inevitable. Further, the electrode structure shown in this document has a sandwich structure made of a homogeneous metal, and does not disclose characteristics or the like in the case of using a bimetallic metal.

The concept of memory using pores is proposed only in Non-Patent Document 17, and its history is very short. In this non-patent document 17, too, the grain boundaries of the polycrystalline thin film are merely regarded as pores. There is a report on a CB-RAM (Conductive-Bridge Random Access Memory) using a nanoporous material, and there is a technique using a porous alumina body and a porous silica body. However, since these porous bodies have a very large pore diameter distribution, there are variations in operating current and the like. In addition, since it is an anodic oxidation process, manufacturing itself is a method of high degree of difficulty. There is no report of CB-RAM using this method.

In the memory using pores, it is preferable to use one pore as one memory cell from the viewpoint of high density, but control of the pore size and pore interval is the key to practical use. From such a point of view, although use of a porous article with precise control of pores is considered, there is a problem such as thinning of zeolite, and at present, there is no report of CB-RAM using zeolite.

(2) the pore diameter is small (the cell size is small and the density can be reduced); (3) it is easy to form a thin film, and the like . The CB-RAM takes the structure of electrode A / memory layer / electrode B, electrode A is electrochemically active and ionizable metal, and electrode B is electrochemically stable metal. By applying a voltage between the electrodes, the atoms constituting the electrode A are diffused in the memory layer, and the resistance is switched to low resistance / high resistance by the formation / insulation of the filament type bridge. By using a porous polymeric metal complex in the memory layer, high performance of the CB-RAM using the excellent characteristics (1) to (3) is expected.

In the CB-RAM, since the formation of the filament made of copper metal is caused by the diffusion of the electrode constituting metal in the memory layer, and the low resistance / high resistance is switched by this, It is often necessary to promote metal diffusion (or metal ion diffusion). However, it is difficult to form metal nanowires, that is, filaments because the porous polymer metal complex or CB-RAM has low conductivity and a very small temperature rise due to the joule heat. In addition, There is no report on CB-RAM using porous polymer metal complexes, although there are very few reported cases of ReRAM involving fracture.

International Publication No. 2013/161452 Japanese Patent No. 4834048

Susumu Kitagawa, Integrated Metal Complex, Kodansha Scientific, 2001, pp. 214-218 Yaghi et al., Science (2008) 939 Rosseinsky et al., Microporous and mesoporous Mater. 73, (2004), 15 AFM3885_14Volkmer Veciana / maspoc et al., Chem. Soc. Rev. (2007) 36, 770 Janiak et al. Dalton trans. (2003) 2781 Kepert, C, J et al. Chem. Commun. (2006) 695 3 JANUARY 2014 VOL 343 SCIENCE Allendorf Dunbar, AG6543_11 Kitagawa et al., IC172_11Kitagawa SusumuKitagawa170_JACS16416_06 SusumuKitagawa195_JACS10990_07 Sakata et al., Science 2013, 339, 193-196. Kaneko et al., Jacs2112_10kaneko Long / Yaghi, JACS14522_11Long AFM2677_15 Li S. Hasegawa, K. Kinoshita, S. Tsuruta, S. Kishida, ECS Trans. 2013, 50, 61. Chem. Commun. (2006) 4767

An object of the present invention is to provide a novel porous polymer metal complex conductor obtained by adding a conductive auxiliary agent to a porous polymeric metal complex and a micro switch composed of two kinds of electrode metals. It also provides a memory using the switch.

The present invention is as follows.

(1) A micro switch comprising a first electrode, a second electrode, and a porous polymer metal complex conductor,

Wherein the porous polymer metal complex conductor is represented by the following formula (1)

Wherein a redox potential is different between a metal constituting the first electrode and a metal constituting the second electrode.

[ML_x]_n(D)_y (One)

Wherein M represents a metal ion selected from Groups 2 to 13 of the Periodic Table of the Elements and L represents a ligand capable of forming two or more functional groups capable of coordinating to M and capable of crosslinking with two of M , And D represents a conductive auxiliary agent not containing a metal element. x is 0.5 to 4, and y is 0.0001 to 20 for x. n represents the number of repeating units of constituent units of [ML _x ], and n is 5 or more.

(2) The micro switch according to (1), wherein D is a compound having a carbon-carbon multiple bond in its molecule and containing a sulfur or nitrogen atom.

(3) a compound in which D is a carbon-carbon multiple bond in the molecule and the carbon-carbon multiple bond is bonded to an electron-withdrawing group or an electron-donating group, or an aromatic compound in which a conjugated system is developed, .

(4) The micro switch according to (2) or (3), wherein the D is an acceptor compound selected from the group consisting of tetracyanoethylene, tetracyanoquinodimethane, benzoquinone, and derivatives thereof.

(5) The micro switch according to (2) or (3), wherein D is a donor compound selected from tetrathiafulvalene or derivatives thereof.

(6) The micro switch according to any one of (1) to (5), wherein the porous polymer metal complex conductor contains at least two of the above-mentioned D.

(7) The micro switch according to (6), wherein at least one of the two or more species D is an organic conductive auxiliary agent comprising an organic substance having a charge in a molecule.

(8) The micro switch according to (7), wherein the organic conductive auxiliary agent is selected from the group consisting of a quaternary ammonium salt, a phosphonium salt, an amine-alkali metal ion complex, an imidazolium salt, a pyridinium salt and a sulfonium salt. .

(9) The micro switch according to any one of (1) to (8), wherein the content of D is 0.001 to 30 mass% with respect to the porous polymer metal complex conductor.

(10) The method according to any one of (1) to (9), wherein the M is a divalent, trivalent or tetravalent metal ion selected from chromium, manganese, iron, cobalt, nickel, copper, Smile switch.

(11) The micro switch according to any one of (1) to (9), wherein L is an aromatic compound containing two or more carboxyl groups in the molecule.

(12) The micro-switch according to any one of (1) to (9), wherein L is a non-aromatic compound containing two or more carboxyl groups in the molecule.

(13) The micro switch according to (11), wherein L is an aromatic compound containing two or more nitrogen atoms of a satellites in a molecule.

(14) The micro switch according to (12), wherein L is a nonaromatic compound containing two or more nitrogen atoms of a satellites in a molecule.

(15) The method according to any one of (15) to (16) above, wherein M is at least one element selected from the group consisting of magnesium, aluminum, calcium, scandium, manganese, iron (II), iron (III), cobalt, nickel, copper, zinc, zirconium ruthenium, rhodium, ≪ / RTI >

Wherein L is a substituted or unsubstituted terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 2.7-naphthalene dicarboxylic acid, 4.4'-biphenyldicarboxylic acid, The micro switch according to any one of (1) to (9), wherein the micro switch is selected from the group consisting of 4'-bipyridine, 1,4- (4-pyridyl) benzene and substituted or unsubstituted imidazole.

(16) The micro switch according to any one of (1) to (15), wherein the difference between the redox potential of the metal constituting the first electrode and the metal constituting the second electrode is 0 eV to 5.0 eV.

(17) The organic electroluminescent device according to any one of (17) to (17), wherein the metal constituting the first electrode is a metal selected from the group consisting of Au, Pt, W, Ru, In, Rh,

The micro-switch according to any one of (1) to (16), wherein the metal constituting the second electrode is a metal selected from the group consisting of Cu, Ag, Zn, Co, Mn and Al.

18 is the metal constituting the first electrode, indium tin oxide _{(ITO: Tin-doped In 2} O 3), doped with Nb titania, SrTiO doped with Ga or zinc oxide, and Nb doped with Al ₃ , SrRuO ₃ , RuO _2, or IrO ₂ .

(19) An electronic device configured by using the micro switch according to any one of (1) to (18).

(20) a step of mixing a metal ion and a ligand to form a porous polymer metal complex,

Contacting the porous polymeric metal complex with the first and second electrodes,

A step of mixing the porous polymer metal complex brought into contact with the first and second electrodes and a conductive auxiliary agent to form a porous polymer metal complex conductor

A method of manufacturing a micro switch for a CB-RAM,

The metal ion is selected from Groups 2 to 13 of the periodic table,

The ligand is capable of containing two or more functional groups capable of coordinating with the metal ion within the structure and capable of crosslinking with two of the metal ions,

The conductive auxiliary agent is a material not containing a metal element,

Wherein the redox potential is different between a metal constituting the first electrode and a metal constituting the second electrode.

(21) a step of mixing a metal ion, a ligand, and a conductive auxiliary agent to form a porous polymer metal complex conductor,

A step of bringing the porous polymer metal complex conductor into contact with the first and second electrodes

And a second step of forming a micro switch,

The metal ion is selected from Groups 2 to 13 of the periodic table,

The ligand is capable of containing two or more functional groups capable of coordinating with the metal ion within the structure and capable of crosslinking with two of the metal ions,

The conductive auxiliary agent is a material not containing a metal element,

Wherein a redox potential is different between a metal constituting the first electrode and a metal constituting the second electrode.

The porous polymer metal complex conductor of the present invention and the microswitch formed of two kinds of metals can be used as a memory. The present invention can also be applied to a random access memory, a storage class memory and an integrated circuit (memory chip, LSI), a storage device (SSD, SD card, USB memory, etc.) ) Circuit switching switches, and other devices (sensors).

The micro switch composed of the porous polymer metal complex conductor of the present invention can be applied to various types of devices formed by the present microswitch, such as miniaturization, high integration, power saving, improvement in response speed, , Weight reduction by thinning, simplification of process by facilitating material synthesis, reduction in cost, and commercialization.

The micro switch of the present invention can be used in a programmable circuit. The programmable circuit is a field programmable gate array (FPGA) circuit, which is a kind of gate array in which a user can write his or her own logic circuit, as a concrete example, in which a user can set a circuit in accordance with his / her purpose. Digital signal processing, software radio, avionics, and the like. By using the microswitch of the present invention, further miniaturization and high performance can be achieved.

The micro switch of the present invention can be used in a memory chip. A memory chip is a device in which memory elements are integrated. And is used as a memory element of a personal computer or a mobile device. By using the micro switch mechanism of the present invention, it is possible to achieve high integration and high functionality by miniaturization and the like.

The control device can be configured by using the memory chip using the micro switch of the present invention. The control device is a microcomputer or the like and is used for control of household appliances and the like. By using the present invention, high integration and high functionality due to miniaturization and the like can be achieved.

The LSI can be configured using the micro switch of the present invention. LSI is a large-scale integrated circuit widely used in control devices and the like. At present, silicon-based LSIs are being used practically because oxide films can be manufactured with good quality and P and N types can be easily produced separately. However, by using the micro switch of the present invention, it is possible to realize an LSI by a single PCP like the Si / silicon oxide film. This is because, in addition to the expectation of realizing basic circuit elements such as diodes and transistors in view of the fact that PCP has inherent semiconductor properties and can control the carrier type and carrier concentration by doping, , It is possible to provide a PCP-based storage device necessary for the realization of the LSI. It is also possible to realize an Si substitute LSI by using the microswitch of the present invention from the fact that PCP is easy to form an ultra-thin film or form a fine circuit, and that doping is easy in process and fine doping is possible .

The sensor can be constructed using the micro switch of the present invention. It is known that PCP adsorbs various solvents, water, and the like in pores, and it is known that the characteristics of PCPs change thereby. Using this principle, sensors can be developed by using the change in conductivity and switching voltage depending on solvents, gas molecules, light, and the like.

A neurocomputer having a learning function can be constructed by using the micro switch of the present invention. A neurocomputer is a computer having a learning function in which a circuit is dynamically formed, in which a circuit is formed dynamically, such as formation of a new circuit, elimination of an unnecessary circuit, etc., to be. Is a device that allows a user to voluntarily implement a function that matches a user's preference without actively performing a program. In the microswitch of the present invention, when the formed filament is not used, the constituent metal is gradually diffused and tapered, and when it is used, it becomes thick, so that it is possible to realize a neurocomputer function similar to the memory formation of neurons do.

Artificial intelligence using a neurocomputer using the micro switch of the present invention can be constructed. Artificial intelligence is a general term that artificially implements human-like intelligence. By using the neurocomputer, the artificial intelligence advances spontaneously according to the user's preference, and the robot can be applied to a robot having pattern recognition capability.

Various functions and devices that are made flexible and lightweight can be constructed by using the microswitches of the present invention. The advantage of the flexibility is that the function can be expressed without limiting the shape, such as wearables. The micro switch of the present invention has the flexibility, thin film and light weight of the organic material, so that the micro switch can be made flexible and lightweight.

1 is a graph showing the evaluation of data write / erase and data retention characteristics of a memory element manufactured from the micro switch of the present invention.
2 is a schematic view showing the shape of pores present in the porous polymeric metal complex.
3 is a schematic diagram of anisotropy of pores.
4 is a diagram showing an example of a device structure and a circuit constructed by using the micro switch of the present invention.
5A is a diagram showing an example of the structure of the micro switch.
5B is a diagram showing an example of the structure of the microswitch.
5C is a diagram showing an example of the structure of the microswitch.
5D is a diagram showing an example of the structure of the microswitch.

The microswitch proposed by the present invention is a microswitch in which a porous polymer metal complex conductor obtained by adding a conductive auxiliary agent to a porous polymeric metal complex is formed into an electrode composed of two kinds of metals electrochemically having different oxidation- And an electrode composed of an active metal and an inert metal). Thereby, it is possible to intentionally switch the high resistance and the low resistance electrically.

The present invention makes use of a circuit composed of a porous polymer metal complex conductor and two kinds of metals having different oxidation-reduction potentials, thereby making it possible to use diffusion of the electrode metal in the nanopores of the porous polymer metal complex conductor, Function as a microswitch by associating a state in which the electrodes are connected by the electrode metal and a state in which the electrodes are adhered to "1" and "0". With this structure, it is possible to realize a microswitch function without irreversible destruction of the porous polymer metal complex conductor. Therefore, it is possible to realize a micro switch function, a characteristic surface such as a reduction in operating current, stabilization, Is excellent.

The micro switch of the present invention can be used as a nonvolatile memory such as ReRAM. Both ReRAM and CB-RAM seem to be similar in that the switching of resistance is realized by the formation of a conductive path and the adiabatic effect. However, it is reported that the conductive path of ReRAM is composed of oxygen deficiency. In contrast, CB-RAM is composed of a metal atom, and has excellent current-carrying characteristics and is suitable for circuit switching switches for FPGA (Field Programmable Gate Array) Application can be made.

The present invention can also be applied as an LSI technique for locally doping p-type and n-type dopants, and for applying not only memories but also circuit elements such as transistors and diodes to PCP substrates. In order to realize this, an ink jet technology or the like can be used.

DISCLOSURE OF THE INVENTION In order to solve the above-mentioned problems, the inventors of the present invention have conducted intensive research and have found that, as a result, an organic conductive auxiliary agent comprising an organic substance having a charge is added to a porous polymeric metal complex to prepare a polymer metal complex conductor, And it is brought into contact with two types of electrode metals having different oxidation-reduction potentials to constitute a circuit, thereby functioning as a microswitch. Thus, the present invention has been completed. Further, it has been found that the present microswitch functions as a memory, and the present invention has been accomplished.

The microswitch comprising the porous polymeric metal complex conductor of the present invention is characterized in that the microswitch is represented by the following structure (2), in which the ligand L is formed by crosslinking the metal ion M and a porous And comprises a polymer metal complex conductor, a first electrode, and a second electrode.

[ML _x ] _n (D) _y | The second electrode (2)

(Wherein M represents a metal ion selected from Groups 2 to 13 of the Periodic Table of the Elements and L represents a ligand capable of cross-linking two M's by containing two or more functional groups capable of coordinating to M in its structure X represents 0.5 to 4 and y represents 0.0001 to 2. _x represents the number of repeating units of the constituent unit consisting of [ML _x ] , And n is 5 or more)

It is a unique characteristic of the porous polymer metal complex conductor used in the present invention that the electrical resistance value between the first electrode and the second electrode changes by application of a driving voltage or current, and two or more other states exist. For example, referring to the voltage sweep-current measurement diagram of FIG. 1, the resistance value at the time of the set-time voltage is different from the resistance value at the time of the reset-time voltage, and in this voltage sweep- State exists.

In the operation mechanism of the switch element of the present invention, the metal of the first electrode is ionized with the application of a voltage, which diffuses in the pores of the PCP, and the ions receive electrons from the second electrode and are reduced, The metal filament formed once is oxidized by the application of a voltage and is returned to the ions and disappears, thereby realizing the switching function. Therefore, the formation and the thermal insulation of the metal filament are required to diffuse the metal ions of the first electrode metal in the pores. For this purpose, a PCP having a pore diameter capable of diffusing metal ions is used, It is important to increase the carrier concentration by adding an auxiliary agent to promote the diffusion of the metal ions by the temperature rise due to generation of the joule heat.

Further, since the solvent in the pores has a great influence on the voltage (i.e., switching voltage) necessary for ionization of the inert electrode and the diffusion of metal ions, it is necessary to select an appropriate solvent. Since the shape of the filament affects the switching function, it is important to appropriately select the kind of metal species, ligand species, pore shape, and conductivity auxiliary agent of PCP which can affect the shape of the filament.

In addition, a conductive auxiliary agent having a relatively large aspect ratio inside the pores of the porous polymer metal complex conductor changes in rotation or position in the pores with the application of a voltage, so that the effective volume in the pores changes, It is thought that the switch effect is manifested by the change of the pore volume and the generation of the metal nanowire based on the diffusion of the metal ion in the electrode due to the voltage application and the reduction thereof and the disappearance of the metal nanowire based on this reverse reaction do.

The porous polymer metal complex conductor used in the microswitch of the present invention has a network structure. The network structure is composed of the metal ions M and the ligands L. The dimensionality of the network structure may be a one-dimensional structure in which linear polymer complexes are regularly collected, a two-dimensional network structure in a planar shape, a three- All structures can be taken. The actual material, regardless of these dimensions, is a material in which the unit structures are aggregated, and is a crystalline or amorphous solid. In case of one-dimensional structure or two-dimensional structure, material flexibility is shown. In case of three-dimensional structure, fastness of material is shown, but a basic network can be selected according to use.

Since the polymer metal complex conductor used in the microswitch of the present invention is a porous body, if it comes into contact with organic molecules such as water or alcohol or ether, water or an organic solvent is contained in the pores and, for example, The material may be changed.

(ML _x ) _n (D) _y (G) _z |

(Wherein M represents a metal ion selected from Groups 2 to 13 of the Periodic Table of the Elements and L represents a ligand capable of cross-linking two M's by containing two or more functional groups capable of coordinating to M in its structure X is 0.5 to 4, and y is 0.0001 to 2 for x, and G is a solvent molecule used in the synthesis as described below or a metal complex in air Z is a number of 0.0001 to 4 with respect to the metal ion 1. n is the number of repeating structural units composed of [ML _x ], and n is 5 or more)

However, among these composite materials, the guest molecule represented by G is merely weakly bonded to the polymer metal complex conductor, and is easily removed by vacuum drying or the like when used in a switch. Thus, the guest molecule represented by the formula (2) Lt; / RTI > Therefore, even in the form represented by the formula (3), it can be regarded essentially as a micro switch similar to the micro switch of the present invention. When G is a substance in such an amount that does not affect the physical properties of the microswitch, it can be used as it is while containing G. On the other hand, in the case where G is a molecule, for example, water, which assists in the pore movement of the ionic substance, it is possible to use this switch in a form containing G positively.

≪ Synthesis method of porous polymer metal complex conductor >

The porous polymeric metal complex conductor of the present invention can be produced as follows. The porous polymer metal complex conductor represented _by [ML _x ] _n (D) _y in the formula (1) can be obtained by adding the conductive auxiliary agent D to the porous polymer metal complex represented by the formula (4).

[ML _x ] _n (4)

(Wherein M, L, and x are as defined above, n represents the number of repeating structural units of [ML _x ], and n represents 5 or more)

As the porous polymer metal complex represented by the formula (4), a known porous polymer metal complex synthesized by a known method can be used. Specifically, it can be obtained by a reaction in a solution or solid phase of a metal ion and a ligand.

The method of preparing the porous polymeric metal complex has various conditions and can not be determined uniquely. Generally, the metal ion source includes a metal salt (e.g., copper nitrate), a metal (copper or the like), a metal oxide Copper and the like) and a ligand, an organic compound having two or more coordination sites such as aromatic carboxylic acids such as terephthalic acid and trimesic acid, aliphatic carboxylic acids such as fumaric acid and citric acid, imidazole, 4,4'- And compounds having an aromatic nitrogen functional group such as bipyridine and substituted compounds thereof. Examples of the reaction conditions include a solution method using a solvent such as water, alcohol or DMF, or a solid phase method without using a solution. For example, Cheetham et al., Angew. Chem. Int. Ed. (2010) 9640, Yaghi et al., Science (2009) 855, Sigma-Aldrich's pamphlet, Fundamentals of Materials Science 7.

≪ Method of Adding Conductive Adjuvant to Porous Polymer Metal Complex >

The polymeric metal complex conductor can be obtained by adding the conductive auxiliary agent D to the porous polymeric metal complex represented by the formula (4). A method of adding a substance comprising a porous polymeric metal complex and a conductive auxiliary agent dissolved in a solution, a method of immersing a porous polymeric metal complex in a solvent in which a conductive auxiliary agent is dissolved, introducing a solvent in which the conductive auxiliary agent is dissolved in the pores, A method in which a porous polymer metal complex and a conductive auxiliary agent are mixed and added in a solid phase; a method in which a conductive auxiliary agent is a liquid; a method in which a conductive auxiliary agent is mixed with a porous polymeric metal complex without using a solvent; A method in which a metal ion as a raw material of a porous polymeric metal complex, a substance comprising a ligand, and a conductive auxiliary agent are reacted in a liquid or solid phase and added.

The method of dissolving the conductive auxiliary agent in a solution and adding it has the advantage that it can be carried out under mild conditions. The method of adding in the solid phase does not require a solvent, and the method of adding the conductive auxiliary agent by vaporizing has an advantage that the conductive auxiliary agent is highly purified at the time of vaporization. The method of adding a metal ion, a ligand material, or a conductive auxiliary agent as a raw material of a porous polymeric metal complex in a liquid or a solid phase by reacting may include adding a conductive auxiliary agent to a porous polymeric metal complex having a pore window smaller than that of the conductive auxiliary agent . Considering these advantages, the addition method can be selected depending on the kind of the porous polymer metal complex and the conductive auxiliary agent to be used and the use of the obtained material.

<Conductive auxiliary agent D>

It is necessary to add the conductive auxiliary agent D in order to impart conductivity to the porous polymeric metal complex having low conductivity. Examples of the material capable of imparting conductivity to the porous polymeric metal complex include a substance that performs oxidation and reduction by itself, such as ferrocene. However, the redoxic material may be a metal nanowire formed in the pores of the porous polymer metal complex So that there is a possibility that the switch function is deteriorated. For this reason, organic materials having a carbon-carbon multiple bond in the molecule and having a charge such as a donor type or acceptor type substance containing a hetero atom such as sulfur or nitrogen or tetramethylammonium tetrafluoroborate are preferable.

Further, the conductive auxiliary agent D does not contain a metal element. Ferrocene or the like is used as the conductive auxiliary agent D, it is not preferable because the metal element inhibits the heat generation of the metal wire and the resulting wire.

Examples of the substance used as the conductive auxiliary agent D include a substance having a carbon-carbon multiple bond in its molecule and containing a hetero atom such as sulfur or nitrogen.

Alternatively, as the material used as the conductive auxiliary agent D, a conductive auxiliary agent having a carbon-carbon multiple bond in the molecule and having an electron-attracting group or an electron-donating group bonded to the carbon-carbon multiple bond, or a conductive auxiliary agent having a conjugated system Aromatic compounds. Examples of the electron-withdrawing group or electron-donating group include a cyano group, a carbonyl group, an amino group, an imino group, and a sulfur atom. The aromatic compound in which the above conjugated system is developed refers to a substance which is conjugated with at least seven double bonds or triple bonds and which is regarded as an aromatic compound because it satisfies the Finkel's rule. This material enables the non-localization of electrons by the presence of multiple conjugated double bonds, triple bonds. As the aromatic compound in which the conjugated system has been developed, for example, fullerenes can be cited.

The carbon-carbon multiple bond imparts conductivity to the porous polymeric metal complex through interaction with the metal ion M contained in the porous polymeric metal complex or with a heteroatom such as oxygen or nitrogen contained in the ligand L . It is also believed that the heteroatoms such as sulfur and nitrogen in the conductive adjuvant cause electrons to be biased to the carbon-carbon multiple bonds in the conductive adjuvant to enhance the interaction between the porous polymeric metal complex and the conductive adjuvant.

Specific examples of the conductive auxiliary agent D include bis (ethylene dithio) tetrathiafulvalene, bis (methylenedithio) tetrathiafulvalene, bis (trimethylene dithio) tetrathiafulvalene, bis (Ethylene dithio) tetrathiafulvalene-d ₈ , dimethyl tetrathiafulvalene, formyl tetrathiafulvalene, phthalocyanines, tetrathiafulvalene, tetrakis (methylthio) tetrathiafulvalene, tetrakis ) Tetrathiafulvalene, tetrakis (dimethylamino) ethylene, tris (tetrathiafulvalene) bis (tetrafluoroborate) complex, tetrakis (ethylthio) tetrathiafulvalene, tetrathiafulvalene- 8,8-tetracyanoquinodimethane complex, 2,3,6,7-tetrakis (2-cyanoethylthio) tetrathiafulvalene and the like.

Among these materials, bis (ethylene dithio) tetrathiafulvalene, bis (methylenedithio) tetrathiafulvalene, tetrakispulvalene, tetrakispulvalene in view of being small and capable of being added to porous polymer metal complexes having various sizes of pores, (Dimethylamino) ethylene, tetrathiafulvalene-7,7,8,8-tetracyanoquinodimethane complex, and the like can be suitably used. However, when the porous polymeric metal complex contains copper ions, the interaction of the tetracyanoquinodimethane with the copper ion is strengthened, and the mobility of the conductive auxiliary agent in the pores is lowered. As a result, It is preferable to use a conductive auxiliary agent other than tetracyanoquinodimethane when the porous polymeric metal complex contains copper ions.

Examples of the substance providing the acceptor molecule include substituted or unsubstituted 1,4-benzoquinones, bis (tetrabutylammonium) bis (malononyldithiolato) nickel (II) complexes, 1,3-bis Bis (tetrabutylammonium) bis (1,3-dithiol-2-thione-4,5-dithiolato) palladium (II), bis (tetrabutylammonium) tetracyano diphenoquinone Nordimanide, substituted and unsubstituted fullerenes, 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, 7,7,8,8-tetracyanoquinodimethane, tetrafluoro Tetracyanoquinodimethanes such as rutetracyanoquinodimethane and 11,11,12,12-tetracyanoantho-2,6-quinodimethane, tetracyanoethylene, 3,3 ', 5, 5'-tetra-tert-butyl-4,4'-diphenoquinone.

Among the above materials, it is preferable to use a substituted or unsubstituted 1,4-benzoquinone, bis (tetrabutylammonium) bis (malononitrile) in view of being capable of being added to a porous polymer metal complex having small pores and various sizes of pores Dithiolato) nickel (II) complex, 1,3-bis (dicyanomethylidene) indane, bis (tetrabutylammonium) tetracyano diphenoquinodimanide, 2,3-dichloro-5,6-dicyano 1,4-benzoquinone, 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, and 7,7,8,8-tetracyanoquinodimethane are suitable Can be used.

In particular, the conductive auxiliary agent having a tetratriafulvalene skeleton is excellent in that the durability of the material is improved. In particular, tetracyanoethylene and a conductive auxiliary agent of the tetracyanoquinodimethane type substituted with a functional group are excellent in that the response speed is high.

It is also preferable to add an organic substance having a charge such as an ionic liquid to the conductive auxiliary agent D. [ Quaternary ammonium salts such as tetraethylammonium tetrafluoroborate, phosphonium salts such as tributylhexadecylphosphonium bromide, the same amine-alkali metal ion complexes of sodium dicyanamide, 1-butyl-3-methylimidazolium bromide , Imidazolium salts such as 1-butyl-3-methylimidazolium iodide and 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-aminopyridinium iodide, Pyridinium salts such as di-n-octyl-4,4'-bipyridinium dibromide, piperidinium salts such as 1-butyl-1-methylpiperidinium bromide, triethylsulfonium bis (trifluoromethane And sulfonium salts such as sulfonyl imide. In addition, pyridinium salts, ammonium salts, sulfonium salts and phosphonium salts can be suitably used because they have strong ionic interaction with the conductive auxiliary agent D and can enhance the conductive performance. In particular, the conductive adjuvants of the ammonium salt and pyridinium salt type are superior in terms of durability of the memory function.

The conductive auxiliary agent D may be used in a mixture of two or more kinds, depending on the application.

The content of the conductive auxiliary agent D is preferably 0.001 to 30 mass%, more preferably 0.005 to 15 mass% with respect to the porous polymer metal complex conductor.

<Metal ion M>

The porous polymer metal complex [ML _x ] used in the microswitch of the present invention is formed of a metal ion M and a ligand L. The choice of metal ion M species affects switching characteristics.

The metal ion M constituting the porous polymeric metal complex used in the microswitch of the present invention is a divalent, trivalent or tetravalent metal ion selected from Groups 2 to 13 of the Periodic Table of the Elements. Chromium, manganese, iron, cobalt, nickel, copper, zinc, cerium, scandium, zirconium, ruthenium, rhodium, cadmium and rhenium are preferable from the viewpoint of forming a highly stable porous polymer metal complex. Iron, cobalt, nickel, copper, zinc and zirconium are preferable from the viewpoint of high affinity with the conductive auxiliary agent and high easiness of conductivity. Chromium, manganese, iron, cobalt, nickel, zinc, cerium, scandium, zirconium, ruthenium, rhodium, cadmium and rhenium can be suitably used in view of the high response speed of the memory effect. Iron, cobalt, nickel, zinc, and zirconium are preferable in that the durability of the micro switch (switching element) is high. These metal ions M may be used by mixing two or more kinds thereof.

When the metal ion M is a copper ion and copper is used as the active metal of the electrode, the copper ion in the PCP tends to deteriorate because the copper ion eluted from the electrode metal becomes a nanowire , And metal ions other than copper are preferable.

The porous polymeric metal complex used in the microswitch of the present invention is formed of a metal ion M and a ligand L. The ligand L species affects the switching characteristics. Hereinafter, the description will be given.

&Lt; Ligand L >

The ligand L is a ligand capable of containing two or more functional groups capable of coordinating to the metal ion M in its structure and capable of crosslinking with two metal ions M.

Examples of such ligand materials include dicarboxylic acids such as substituted and unsubstituted terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid, substituted and unsubstituted trimesic acid, Tricarboxylic acids such as 2,4-naphthalenetricarboxylic acid and 2,5,7-naphthalenetricarboxylic acid, substituted and unsubstituted 1,2,4,5-benzenetetracarboxylic acids, 1,4 , Tetracarboxylic acids such as 5,8-naphthalenetetracarboxylic acid and the like, substituted or unsubstituted 4,4'-bipyridine, bipyridyl such as 1,4- (4-pyridyl) benzene, Substituted imidazoles, and benzimidazoles.

Dicarboxylic acids such as substituted and unsubstituted terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid and 4.4'-biphenyldicarboxylic acid, and substituted and unsubstituted dicarboxylic acids such as substituted and unsubstituted dicarboxylic acids , Unsubstituted 4,4'-bipyridine, and 1,4- (4-pyridyl) benzene can be suitably used. These ligands may be used in a mixture of two or more kinds.

The ligand material in which two carboxyl groups are bonded to the benzene ring, such as terephthalic acid and isophthalic acid, has a low electron density of the benzene ring, so that the interaction with the metal ion becomes small, and the diffusion rate of the metal ion, , The dissolution rate is improved, and the response speed is improved.

The combination of acidic ligand materials of different sizes and basic ligand materials, such as biphenyldicarboxylic acid and DABCO (1,4-diazabicyclo [2.2.2] octane), is preferred because the porous polymeric metal complex having anisotropic pores is obtained It is preferable because it is easy.

There are three types of pores of the formed porous polymer metal complex, one-dimensional, two-dimensional and three-dimensional. Fig. 2 is a conceptual diagram thereof. When the crystal lattice is assumed to be a cubic body, it is a three-dimensional pore that one-dimensional pores exist in only the opposite surface, two-dimensional pores exist in the four surfaces, and through holes exist in all six surfaces. There is no direct relation to the dimensionality of the network structure and the dimensionality of the pore. The network structure or the size of the ligature is a three-dimensional network structure, which has three-dimensional pores, two-dimensional pores, one- Lt; / RTI &gt; As described above, the dimensional structure of the network structure influences the flexibility of the porous polymeric metal complexes, but the dimensional purity of the pores affects the diffusion of the metal ions in the pores and the growth of the nanowires. As a result, .

In the three-dimensional pores, active metal ions are highly diffusible, and nanowires can grow in many directions, so that a material having high conductivity is obtained, and the response speed is excellent. Further, it is excellent in that CB-RAM of a cross point can be formed by using the feature that the nanowires extend in many directions, that is, the problem of wiring to the memory device can be solved.

Since the direction of growth of nanowires is limited in the two-dimensional pores compared to the three-dimensional pores, a smaller fine switch can be designed. Since the direction of growth of the nanowire is limited more than that of the two-dimensional pores, the one-dimensional pores enable the design of a finer switch, the nanowire becomes a linear shape, and the stiffness is lowered. The occurrence of stress on the porous polymer metal complex accompanied with the reduction of the stress is reduced and the repetitive characteristics are excellent.

<Anisotropy of workpieces>

As shown in Fig. 3, when the crystal lattice is assumed to be a cubic body, the case where the pore diameters opened on each surface are not the same is anisotropic pores. The open pore diameter on each side is the isotropic pore. By using the anisotropic pores, it is possible to grow the metal nanowires in only one direction, even if the dimensionality of the pores is three-dimensional, and the same effect as in the case of using the porous polymer metal complex having two-dimensional pores or one- May be obtained.

In the case of using PCP having anisotropic pores as shown in Fig. 3, the conductive auxiliary agent can be locally doped. For example, when a certain conductive auxiliary agent (hereinafter referred to as conductive auxiliary agent a) is immersed in the entire porous polymer metal complex and the porous polymer metal complex containing the conductive auxiliary agent a is immersed in a solvent or the like, Since the diameter is large, the conductive auxiliary agent a escapes only in the vertical direction. As a result, it becomes possible to add the conductive auxiliary agent in the form of a layer at the center of the crystal. Since this material is immersed in a separate conductive auxiliary agent (hereinafter referred to as conductive auxiliary agent b) this time, the conductive auxiliary agent b enters only from the upper and lower directions in which the pore diameters are large, it is possible to form a b layer.

When doping of the conductive auxiliary agent a, undoping using the anisotropy, and dope operation of the conductive auxiliary agent b in the anisotropic porous polymer metal complex formed on the metal substrate, the conductive auxiliary agent is removed only in the direction in which the substrate is not present Since the doping is carried out, a laminate of the dopants a and b is obtained. The pnp connection and the pn connecting element can be formed by making the dopants a and b each a p-type n-type.

<Influence of pore diameter>

A porous polymer metal complex having a large pore diameter has a high diffusibility of electrode metal and a thick metal nanowire, so that a material excellent in response speed can be obtained. The porous polymer metal complex having a small pore diameter has a low diffusion property of the electrode metal and forms a thin metal nanowire, so that the response speed of the material is low, but the cell size can be made small, . Further, since the metal nanowires are thin, the generation of stress on the porous polymer metal complex accompanying nanowire formation and disappearance is small, and the durability of the material is excellent.

<Bearing of handwork>

In addition to the pores having an anisotropic three-dimensional structure, it is necessary that pores exist in the direction in which the metal nanowires are grown between the active metal electrode and the counter electrode. For example, even if the one-dimensional pores exist in parallel with the active metal electrode, no conductivity is obtained, and no memory effect is produced. In order to grow the pores in the direction in which the metal nanowires are grown between the active metal electrode and the counter electrode, a method of controlling the conventional crystal orientation such as addition of carboxylic acids or utilization of an anchor layer can be used. It is also possible to confirm the orientation of the pores in the crystal by the thin film X-ray.

<Description of PCP network structure and switching characteristics>

The network structure of the PCP affects conductivity and switching characteristics. The three-dimensional PCP is a PCP in which the network structure is composed of a ligand and a metal ion in a three-dimensional clogging state. The three-dimensional PCP is excellent in fastness because of its structure. That is, it is excellent in terms of characteristics of durability of memory.

The two-dimensional type PCP is, for example, a PCP in which the network structure formed of a metal ion and a ligand, such as a network, is two-dimensional. The network structure itself is two-dimensional, but many of these are stacked to form a crystal structure. Since only weak intermolecular interaction acts between each two-dimensional network, each network can be slightly deviated from each other, and the flexibility is comparatively excellent. Therefore, even when the film is made thin, it is excellent in that cracks do not easily occur due to external stress.

One dimensional PCP is a PCP in which the network formed by metal ions and ligands has a linear structure. The network structure itself is one-dimensional, but many of these are stacked to form a crystal structure. Since each one-dimensional network has only weak intermolecular interaction, and each network can be displaced from each other, flexibility is excellent. Therefore, stress is hardly accumulated in the material even if the nanowire is repeatedly formed and removed, and defects such as stress cracks are unlikely to occur.

&Lt; Method of forming a porous polymer metal complex conductor layer >

In the present invention, a porous polymer metal complex conductor layer is formed on a substrate.

&Lt; Thickness &

The layer thickness of the porous polymer metal complex conductor can be determined depending on the application. When used as a memory, it is preferably from 0.1 to 1000 nm, and from a speed of a response speed is preferably from 0.3 to 600 nm, more preferably from 1 to 500 nm.

<Formation method>

The porous polymer metal complex conductor layer can be formed by various known methods.

(1) Immersion method

The dipping method is a method in which a substrate (for example, a noble metal such as Au, Pt, W, Ru, In or Rh, silicon or a transition metal such as Cu, Ag, Zn, (Hereinafter referred to as &quot; anchor material &quot;) with a substance (hereinafter referred to as &quot; anchor material &quot;) that forms a base for forming a porous polymeric metal complex in a porous material such as alumina (Hereinafter referred to as a &quot; layer &quot;) is formed, and this is immersed in a solution containing a ligand material and a metal ion as a raw material of the porous polymeric metal complex.

As a variant, there is a method in which a substrate having an anchor layer formed thereon is immersed alternately in a ligand solution and a metal ion solution to form a porous polymer metal complex layer by a stepwise method. This method is suitable in that the thickness can be precisely controlled.

The material usable as the anchor material includes a material having a functional group having affinity for the substrate at one end of the molecule and a functional group having affinity for the porous polymeric metal complex at one end of the opposite.

Examples of the functional group having affinity for the substrate include thiol, carboxylic acid, phosphoric acid, sulfonic acid, amino group, pyridyl group and the like. Examples of the functional group having affinity for the porous polymer metal complex include carboxylic acid, phosphoric acid, sulfonic acid, amino group, and pyridyl group.

Specific examples of the anchor materials include normal hexane having a SH group at the first position and carboxyl group at the sixth position, SH group at the first position, normal hexane having the pyridyl group at the sixth position, n-hexane having the SH group at the first position, . The anchor material does not necessarily have a hexyl group, and linear or branched chain alkyl chains or aromatic compounds having various lengths can be used.

Examples of the material used as the anchor layer include organic materials having functional groups at both ends of the molecule. That is, a compound having a functional group such as thiol having an interaction with a metal at one end and a carboxyl group or a pyridyl group capable of interacting with the metal ion at the other end is preferable.

Specific examples include alcohols such as 2-mercaptoethanol, 3-mercaptopropanol, 4-mercaptobutanol, 5-mercaptopentanol, 6-mercaptohexanol, and 12- Mercaptohexanoic acid, 12-mercaptododecanoic acid, 12-mercaptododecanoic acid, 4- (2-mercaptohexanoic acid, 2-mercaptocarboxylic acid, Benzoic acid, 4- (4-mercaptobutyl) benzoic acid, and 4- (12-mercaptundecane) benzoic acid.

From the viewpoint that the porous polymeric metal complex is densely formed, the above-mentioned alcohols, carboxylic acids and the like having an alkyl group of 4 to 12 carbon atoms and a n-alkyl-terminal carboxylic acid having a thiol group at the terminal and having 4 to 18 carbon atoms are suitably used .

The thickness of the anchor layer is preferably from 0.5 to 400 nm, more preferably from 1 to 40 nm, since the porous polymer metal complex is densely formed. In addition, from the viewpoint of not lowering the conductivity, 0.3 to 120 nm is preferable, and 2 to 20 nm is more preferable.

There is also known a method of directly forming a porous polymer metal complex on a substrate without forming an anchor layer. Also in this case, there is known a method in which the substrate is immersed in a solution containing both a metal ion and a ligand material, and a method in which a substrate is immersed alternately in a solution containing either a metal ion or a ligand material.

As a modified method of forming the porous polymer metal complex layer by using the above solution, the substrate is immersed in a ligand material solution containing no metal ion, and the reaction between the substrate and the ligand material or the reaction of the metal And a method of forming a porous polymer metal complex layer by the reaction with an ion without adding a metal salt. This method is preferable in that it can form a very dense porous polymer metal complex layer.

As a similar method, a method of forming a porous polymer metal complex layer by a reaction between a metal oxide and a ligand material can be mentioned. In the case of using this method, a material having a metal oxide layer on the surface of the substrate can be used. The thickness of the metal oxide layer may be selected depending on the application, but is preferably from 0.1 to 1000 nm, more preferably from 1 to 500 nm, from the viewpoint of forming a dense porous polymer metal complex layer.

(2) Spray method

Instead of immersing the substrate in a solution capable of forming a porous polymer metal complex layer, a method of spraying a solution capable of forming a porous polymer metal complex layer on a heated or non-heated substrate may be used. As the spraying method, a known method such as general spraying or spraying by an inkjet method can be used. Also in this method, a method of forming an anchor layer is also available.

(3) Application method

As a method other than the above, there is also a method of applying a slurry containing a ligand material, a metal ion, and the like to form a porous polymer metal complex layer on a substrate. As a coating method, a known method such as dip coating and spin coating can be used.

&Lt; Process for preparing porous metal complex conductor &

The porous polymeric metal complex conductor of the present invention can be prepared by adding a conductive auxiliary agent to the porous polymeric metal complex.

As a method of adding the conductive auxiliary agent to the porous polymeric metal complex, the following methods can be mentioned.

(1) impregnation method

And impregnation method in which a porous polymer metal complex is impregnated in a solution in which the conductive auxiliary agent is dissolved. The impregnation method is excellent in that various conductive auxiliary agents can be added to the porous polymeric metal complex. Further, the addition amount of the conductive auxiliary agent is also excellent in that it can be controlled by controlling the concentration of the conductive auxiliary agent, the impregnation time, and the temperature.

(2) Easy Bottle Method

As another method, a method of introducing a conductive auxiliary agent into the pores of the porous polymeric metal complex by coexisting with a conductive auxiliary agent when synthesizing the porous polymeric metal complex is also cited. Although it is not known how to introduce the conductive auxiliary agent into the pores of the porous polymer metal complex by the easy-bottle method, a simple method of introducing the catalyst into the pores of the porous polymer metal complex is known (Zawarotko et al., J. Am. Chem. Soc., (2011) 10356). Specifically, the method is a method of dissolving a metal salt, a ligand material, and a conductive auxiliary agent which are to be a raw material of a porous polymeric metal complex in a solution, and preparing a porous polymeric metal complex by warming or the like.

There are some pores in the porous polymer metal complex. In such a porous polymer metal complex, the conductive auxiliary agent may not enter into the pores due to interfering with the constricted portion. According to this method, however, this type of porous polymer metal complex It is possible to introduce the conductive auxiliary agent into the pores of the substrate. As a result, a large amount of the conductive auxiliary agent can be introduced into the pores, and a material having an excellent memory holding time tends to be obtained. The amount of the conductive auxiliary agent to be added can be controlled by controlling the amount of the conductive auxiliary agent coexisting in the synthesis.

The present invention is a microswitch formed of two types of electrode metals having different oxidation-reduction potentials from a conductive porous polymeric metal complex. Hereinafter, a description will be given of the two kinds of electrode metals, and a method of forming the metal and the micro switch formed of the porous polymer metal complex conductor will be described below.

&Lt; Electrode metal &

In the microswitch of the present invention, two kinds of metals having different oxidation-reduction potentials are used for the electrode. As the electrode metal, it is preferable to combine metals having a difference in redox potential between 0 eV and 5.0 eV, more preferably 0.01 eV or more and 1.0 eV or less.

Examples of metals usable for the first electrode include Au, Pt, W, Ru, In, Rh, and silicon. These metals are difficult to elute in a solvent and are electrically stable. Pt, Au, Ru, Ir, and W are chemically stable and difficult to melt, and Au and Pt are more preferable because they are electrochemically stable.

Further, as the first electrode, indium tin oxide _{(ITO: Tin-doped In 2} O 3), SrTiO 3, SrRuO 3 doped with a titanium oxide doped with Nb or the like, a zinc oxide doped with such as Ga or Al, Nb, etc. , RuO ₂ , and IrO ₂ can be used.

Examples of the metal that can be used for the second electrode include a metal eluted at a low voltage and composed of an electrochemically active conductive metal and a metal selected from Ag, Cu, Pb, Sn, Zn, Ni, Can be used. Ag and Cu are particularly preferable because they have high conductivity.

It is also possible to use a metal which is difficult to ion-migrate in the pores of the PCP layer to the first electrode and a metal which facilitates ion migration into the pores of the PCP layer to the second electrode. When the first electrode and the second electrode are combined, it is necessary that both the ease of ionization of the electrode metal in the pores of the PCP layer and the ease of ion migration are both the first metal and the second metal.

The thickness of the first electrode and the second electrode may be selected depending on the application, but is preferably 0.1 nm to 100 탆, more preferably 1 nm to 500 nm. In order to miniaturize the memory, the thickness of the first electrode and the second electrode is preferably as thin as possible, and is preferably 500 nm or less. However, in this method, since a method of eluting a metal at the time of forming PCP and using the eluted ions as a raw material of PCP is included, when the electrode is extremely thin, all of the metal is eluted and the electrode disappears There is a concern. Therefore, in order to secure the number of atoms as the supply source of metal ions and obtain stable repetitive characteristics (durability), the thickness of the first electrode and the second electrode is preferably 1 nm or more.

<Configuration of circuit>

As shown in Fig. 4, the circuit configuration includes a laminate type, a flat type, and a sandwich type. The planar type is preferable for circuit formation using the printable technology. The sandwich type is advantageous for high integration. The laminated type is advantageous for increasing the sophistication and functionality of a single layer.

<Method of Forming Micro Switch>

Any method of forming the micro switch shown in Fig. 4 can be used. The first electrode metal and the second electrode metal must be in contact with the porous polymer metal complex conductor. However, the porous polymer metal complex may be in the form of a film or a particle. Further, after preparing the porous polymeric metal complex, the porous polymeric metal complex is converted into the porous polymeric metal complex conductor by bringing the porous polymeric metal complex into contact with one or two kinds of metals and then adding a conductive auxiliary agent thereto to form the microswitch of the present invention You can.

Specifically, for example, the following methods (1) to (4) can be mentioned.

(1) A method of forming a porous polymer metal complex conductor layer on one metal plate of two kinds of metals having different redox potentials and forming the other metal electrode thereon by sputtering, vapor deposition or the like.

(2) A porous polymeric metal complex is formed on one metal plate of two kinds of metal plates having different oxidation-reduction potentials, and a conductive auxiliary agent is applied thereto to form a porous polymeric metal complex. After that, the porous polymeric metal complex is converted into a conductive polymeric metal complex And the other electrode is formed by sputtering, vapor deposition or the like.

(3) a method in which a gap of a bimetallic metal having a different oxidation-reduction potential is previously formed, a porous polymer metal complex in the form of a film or a particle is formed thereon, and a conductive auxiliary agent is applied thereto to convert the porous polymer metal complex into a conductor .

(4) A method of forming a gap of a bimetallic metal having a different oxidation-reduction potential in advance and forming a film or particle-shaped porous polymer metal complex conductor thereon.

<Structure of Micro Switch>

As a structure of the microswitch, there is a structure in which a plurality of electrodes are provided for a porous polymer metal complex conductor (shown as "PCP" in the drawing) as illustrated in Figs. 5A to 5D. As for the position of the electrode with respect to the porous polymer metal complex conductor, in addition to the sandwich structure as shown in Figs. 5A and 5B, a positional relationship as shown in Fig. 5C or a method of installing the same on the same surface as Fig. The structure of any of these can be selected according to the function of the desired microswitch and the structure of the device to be incorporated. However, the structure of Figs. 5A and 5B is preferable in that the structure can be made thin, The structure of Fig. 5A is preferable from the viewpoint of shortening the interval between the electrodes and increasing the response speed, and the structure of Fig. 5D is preferable in view of the fact that the electrodes are on the same plane and are easy to manufacture.

<Access method for smile switch>

A technique used in a conventional NAND flash or the like can be used.

In the microswitch of the present invention, by locally doping the dopant, application to the formation of a circuit, formation of a transistor, and the like becomes possible. Hereinafter, application to formation of a circuit, formation of a transistor, and the like will be described.

<Local doping method and size of dopant>

Local doping of the dopant makes it possible to form a pn junction or the like. The forming method is not particularly limited. Followed by masking using a photolithographic technique, followed by doping by a dipping method. It is possible to form the LSI by locally doping the dopant.

As a local dope method, it is necessary to apply a printerable technique to a MOF (Metal-Organic Framework) film and to dope a target dopant to a local site. When an inkjet is used, dope of about several hundreds nm to several hundreds of micrometers can be performed. However, in order to express the function, it is at least possible to add one molecule of dopant to one cell composed of PCP.

<Method of forming pn junction>

The micro switch of the present invention can be used as a pn junction element by dividing the p-type dopant and the n-type dopant into arbitrary places by the printerable technology.

As another method of dividing, a mask is formed to form a circuit, then a p-type dopant is dipped in, a mask is removed, and an n-type dopant is doped thereinto, and vice versa. Further, since the porous polymer complex has anisotropy, if a p-type dopant is immersed in the solution to prepare a porous polymer complex doped with a p-type dopant and then brought into contact with the solution, a phenomenon of de-dopant occurs from only the specific surface. By using this property, it becomes possible to form a pn junction by doping an undoped region with an n-type dopant.

&Lt; Method of forming transistor &

When the pnp junction and the npn junction are formed in the same manner as described above, the transistor can be used as a transistor.

<Bulk Heterojunction Solar Cell>

By using the above-described technique, it becomes possible to prepare a device in which the number of pn junction surfaces is greatly increased. This material can be used as a high performance bulk heterojunction type solar cell.

The porous polymer metal complex conductor of the present invention is a material obtained by adding a conductive auxiliary agent to a porous polymer metal complex. The conductive auxiliary improves the conductivity by interacting with a metal ion of the porous polymeric metal complex and a portion having polarity such as oxygen or nitrogen contained in the ligand. In addition, the conductive auxiliary agent having a relatively large aspect ratio inside the pores of the porous polymeric metal complex may rotate or change its position in the pores, thereby changing the effective volume in the pores, It is considered that the switch effect is manifested by the change of the volume and the generation of the metal nanowires based on the diffusion of the metal ions in the electrode due to the voltage application and the reduction thereof and the disappearance of the metal nanowires based on this reverse reaction .

It is important that the porous polymer metal complex conductor has a fastness that does not decompose effectively by the application of a voltage. In order to change the rotation or position of the conductive auxiliary agent in the pores and further to generate nanowires, the conductive auxiliary agent has a shape having a relatively large aspect ratio, and a porosity such that the conductive auxiliary agent molecules can move within the pores Of the total amount of water. However, the present invention is not limited to this theory, and the characteristics of the porous polymeric metal complex of the present invention are not limited by this theory.

&Lt; Analysis of Porous Polymer Metal Complex &

There are various conditions for the analysis of the porous polymeric metal complex, and although it can not be determined uniquely, in the case of a single crystal, a single crystal X-ray structure analysis can be used. The known porous polymeric metal complexes can be analyzed by comparing them with a known powder X-ray diffraction pattern by powder X-ray diffraction both in the case of a single crystal and in the case of a powder sample. The porosity of the porous polymeric metal complex can be roughly predicted by measuring the amount of the solvent or the like contained in the pores by thermogravimetric analysis. For the powder X-ray diffraction measurement, a powder X-ray apparatus DISCOVER D8 with GADDS manufactured by Bruker AX Co., Ltd. and a powder X-ray apparatus SmartLab manufactured by Rigaku Corporation can be used. For TG measurement, Rigaku thermogravimetric analyzer TG8120 can be used.

&Lt; Formation of PCP on a substrate >

The porous polymeric metal complex (PCP) can be formed on a substrate as long as it can form a dense porous polymeric metal complex by a known method. For example, by immersing a substrate in a solution in which a ligand and a metal ion are dissolved (Fiscer et al., Chem. Commun. 2009, 1031), a step of immersing a substrate alternately in a solution of a ligand and a metal ion solution to form a porous polymer metal complex (Kitagawa et al., Nature Mater. (2012) 717), a method using a CVD method (Fiscer et al., 2009, 48, 5038) , J. Am. Chem. Soc., 2008, 130, 6119). For the analysis of the film thickness, cross-sectional observation by SEM can be used after general Pt deposition.

&Lt; Evaluation method as memory >

By confirming the resistance hysteresis by voltage sweep-current measurement, the operation as a memory is confirmed. For the measurement, a semiconductor parameter analyzer Agilent 4155C can be used.

The circuit was formed by taking a two-terminal contact into an electrode / PCP / electrode (GND) type device. The contact can be a tungsten coaxial probe of 3 micrometers in diameter, which is available from Japan Micronix HFP-120A-201.

Semiconductor Parameter Analyzer The voltage sweep by the Agilent 4155C is a self-made program by Agilent VEE, with the voltage changing in 20-step steps. Here, the applied voltage is set to 0 to 20 V, the voltage applying speed is set to 64 us / 20 V, and the limiting current value Icomp to prevent device breakdown at set to 1 mA according to the device structure and characteristics. Further, the read voltage V _read of the resistance value R _reg of the memory element is 0.2 V, and is measured at the rise and fall of the voltage in the Set operation and the Reset operation (see Formula A).

R _reg = V (0.2V) / I (0.2V) ... (Formula A)

1 is a graph showing evaluation of data retention characteristics of a memory element manufactured from the micro switch of the present invention. In the evaluation of the data holding property, a voltage of 0.2 V is applied in the reset direction when the resistance is low and in the Set direction when the resistance is high, and the resistance value at that time is derived by the method of (A). The measurement interval was 10 seconds, and the measurement time was 1 minute to 24 hours. The evaluation of the repetitive operation characteristics is confirmed by repeating the voltage application described above.

Example

Hereinafter, preferred examples of the present invention will be described, but the present invention is not limited to these examples. Additions, omissions, substitutions, and other modifications are possible within the scope of the present invention.

Details of the porous conductor, the first electrode and the second electrode of the microswitches of Examples (Inventive Example) and Comparative Examples are shown in the following respective tables. Abbreviations in the table are as follows.

TCNQ: tetracyanoquinodimethane

TCNE: tetracyanoethylene

TTF: tetrathiafulvalene

BEDT-TTF: bis (ethylene dithio) tetrathiafulvalene-tetrathiafulvalene complex

TDAE: tetrakis (dimethylamino) ethylene

BMIB: 1-butyl-3-methylimidazolium bromide

TMATFB: tetramethylammonium tetrafluoroborate

TMAHFP: tetramethylammonium hexafluorophosphate

<Electrochemical Evaluation Items>

<Definition of memory function>

The resistance value in the low resistance state is defined as RL, and the resistance value in the high resistance state is defined as RH, and the memory function is evaluated as follows.

Resistance ratio RH / RL,

100 or more: A

10 or more, less than 100: B

1.5 or more, less than 10: C

Less than 1.5: D

.

<Durability of memory>

The durability of the memory can be defined as the value of evaluation one month later, with respect to the value (initial value) of the I-V evaluation within 3 days after the material is manufactured. A that maintains a value of 80% or more with respect to the initial value, B that maintains a value of 50% or more and less than 80% of B, 30% to less than 50% of C, And D was maintained.

&Lt; Response speed of memory (response speed of switching element) >

The response speed of the memory can be estimated by applying a voltage pulse (or current pulse) having a certain width to the memory element and gradually increasing the pulse height until switching (reset or set) occurs. The judgment criteria of reset or set generation are as shown in (1) definition of memory function.

The relationship between the pulse width, that is, the response speed of the memory and the pulse height is obtained by obtaining the pulse height at which switching occurs with respect to a plurality of pulse widths. By interpolating or extrapolating this relationship, the memory response rate for any pulse height can be estimated. Similarly, it is possible to obtain the relationship between the pulse height and the memory response speed by applying a voltage pulse (or current pulse) having a certain height to the memory element and gradually increasing the pulse width until switching (reset or set) occurs Do. The performance is judged by the following criteria based on the response speed when a pulse voltage of 3V in height is applied.

10 ㎱ or more, less than 1:: A

1 占 퐏 or more, less than 10 占 퐏: B

10 μs or more and less than 100 μs: C

100 μs or more: D

<Holding time of memory>

The data retention time of the memory is determined by monitoring the resistance change of the memory element with a constant voltage or a constant current maintained until the resistance of the memory under the monitor falls out of the range of the resistance value defined as low resistance or high resistance By estimating the time of day. Acceleration tests are often performed by increasing temperature or humidity.

As an evaluation criterion, the time until the deviation from the defined resistance value was evaluated as A, 5000 seconds or more for less than 24 hours, B for 100 seconds or more, C for less than 100 seconds and less than 5000 seconds for 24 hours or more .

&Lt; Number of times of rewriting of memory (number of times of repetition) >

The estimation of the number of times of rewriting of the memory (the number of times of repetition) is carried out by applying voltage sweep (or current sweep) or pulse voltage (or pulse current) and alternately repeating low resistance setting . When the resistance value after applying the voltage sweep (or current sweep) or the pulse voltage (or the pulse current) is not switched within the range of the resistance that is discriminated from the low resistance or the high resistance in the scene where the set or reset should occur, And the number of switching times up to this point is defined as the repeatable number. By repeatedly sweeping the voltage to ± 3 V at a constant speed of ± 1 V / s, a reset is alternately generated. The switching was repeated until the operation became impossible, and the performance was evaluated by dividing the grade of the characteristic by repeating the following conditions.

A: 10 ⁶ times or more

B: Less than 10 ⁶ times to more than 10 ⁵ times

C: Less than 10 ⁵ times to 10 ⁴ times or more

D: 10 Less than ⁴ times

Example 1 (Inventive)

A porous polymeric metal complex, termed HKUST-1, containing a copper ion and having a three-dimensional isotropic network structure is described by Fiscer et al., Chem. Commun. 2009, 1031, except that a thin layer of HKUST-1 (0.1 to 1 micron in thickness) was formed on the electrode in the presence of an electrode metal. Here, the three-dimensional isotropic network structure means a structure in which the crystal structure revealed by the X-ray structure analysis has the same structure in all axes of X, Y and Z. An electrode obtained by laminating the present porous polymeric metal complex on the surface was immersed in a saturated solution of tetracyanoquinodimethane as a conductive additive in dichloromethane for 24 hours at room temperature. An electrode having a porous polymer metal complex conductor formed by adding the conductive auxiliary agent to the surface was formed in a memory circuit by the above-described method, and the memory effect was confirmed by confirming the resistance hysteresis by the voltage sweep-current measurement described above.

In this example, the response speed of the switching element is not a problem, but the durability is low. This is because the tetracyanoquinodimethane of the dopant is small relative to the pore size of HKUST-1, and the interaction of copper ion and tetracyanoquinodimethane contained in HKUST-1 is weak, It is presumed that the tetracyanoquinodimethane of the dopant moves in the pores and the memory effect is lost.

Examples 2 to 10 (Inventive)

A material containing various conductive auxiliary agents was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. [ As a result, I confirmed the memory effect.

Examples 11 to 20 (Examples)

Caskey et al., J. J. Am. Chem. Soc. Porous metallic polymer complexes containing nickel ions and having a three-dimensional isotropic network structure described as &quot; CPO-27-Ni &quot; were synthesized in the same manner as described in Examples 1 to 10 , And the memory effect was evaluated. As a result, we confirmed the excellent memory effect.

Examples 21 to 32 (Inventive)

Kim et al, Angew. Chem. Int. Ed. (2004) 5033, containing a zinc ion and having a network structure of a three-dimensional anisotropy (described as compound 1 in the literature), and synthesized by the method described in the literature, To 10, and the memory effect was evaluated. As a result, we confirmed the excellent memory effect. Here, the network structure of the three-dimensional anisotropy means that the crystal structure revealed by X-ray structural analysis is a structure different from the structure seen from the other axis when viewed from the axis of X, Y or Z.

Examples 33 to 41 (Inventive)

Burrows et al., Dalton Trans. Porous metal complex containing a copper ion and having a two-dimensional network structure (referred to as compound 1 in the literature) described in (2008) 6788 was synthesized by the method described in the literature, Similarly, a conductive material was used to evaluate the memory effect. As a result, excellent memory effect was confirmed.

Examples 42 to 50 (Examples)

Mori et al., Chem. (Described as compound 1 in the literature) containing rhodium ions and having a one-dimensional network structure, described in the literature, Lett., (2002) To 10, a memory effect was evaluated. As a result, excellent memory effect was confirmed.

Examples 51 to 100 (Examples)

As in Examples 1 to 50, porous polymer metal complexes containing various dopants were synthesized to confirm the memory effect. However, instead of adding a conductive auxiliary agent after synthesizing a porous polymeric metal complex as in Examples 1 to 50, Zawarotko et al., J. Am. Chem. Soc., (2011) 10356, a conductive auxiliary agent is introduced into the pores of a porous polymeric metal complex by coexistence of a desired conductive auxiliary agent in a solution for synthesizing the porous polymeric metal complex, , A complex of a conductive auxiliary agent-porous polymer metal complex is synthesized.

The evaluation results of the examples (inventive examples) are shown in the following respective tables.

Comparative Examples 1 to 5

As Comparative Examples 1 to 5, porous metallic polymer complexes were synthesized in the same manner as in Examples 1, 11, 21, 33, and 42, except that no conductive auxiliary agent was added. Table 5 shows the results of these evaluations. In any comparative example, the memory function is evaluated as D. Further, since sufficient memory function was not obtained, the durability and the response speed of the switching element could not be evaluated.

Table 6 and Table 7 show the details of the porous conductor, the first electrode, and the second electrode of the microswitches of Examples (Inventive Example) and Comparative Examples.

Abbreviations in Tables 6 and 7 are as follows.

TCNQ: tetracyanoquinodimethane

BEDT-TTF: bis (ethylene dithio) tetrathiafulvalene

btc: trimesan acid

tpa: terephthalic acid

btb: 1,3,5- (4-carboxyphenyl) benzene

bpy: 4,4'-bipyridyl

Hatz: 3-amino-1,2,4-triazole

Bpe: 1,2-bis (4-pyridyl) ethylene

Dabco: 1,8-diazabicyclooctane

3,6-bis- (pyridin-4-yl) -1,2,4,5-tetrazine

ipa: isophthalic acid

pyz: pyrazine

"Porous polymer metal complex network" in Tables 6 and 7 means dimensionality (one-dimensional, two-dimensional, and three-dimensional) of the skeleton of the porous polymer metal complex. The &quot; pore type &quot; means dimensionality (one-dimensional, two-dimensional, and three-dimensional) of the pores of the porous polymer metal complex.

Example 101

(A compound described as HKUST-1 by Williams et al., Science (1999) 283, 1148), commonly referred to as HKUST-1, in the presence of an active metal, a thin film of HKUST-1 (About 100 microns thick). This material was immersed in a saturated solution of tetracyanoquinodimethane in dichloromethane as a conductive auxiliary for 24 hours at room temperature. An electrode having a porous polymer metal complex conductor formed by adding this conductive auxiliary agent to the surface was formed in a memory circuit by the above-described method, and the memory effect was confirmed by confirming the resistance hysteresis by the voltage sweep-current measurement described above.

Examples 102 to 121

Was synthesized on the surface of an active metal according to the method described in Table 6 and impregnated with a saturated solution of the conductive auxiliary agent 1 shown in Table 6 in the same manner as in Example 101 to obtain an electrode having a porous polymer metal complex conductor on its surface And a memory circuit was formed in the same manner as in Example 101. The evaluation results are shown in Table 8. When the metal ion constituting the porous polymeric metal complex is copper ion, the number of repetition times tends to be relatively low. The reason why the porous polymer metal complex network is three-dimensionally showed a relatively short memory retention time.

Examples 122 to 124

A memory circuit was formed in the same manner as in Examples 102 to 121 by the method described in Table 6. However, the dopants are different from those of Examples 102 to 120. The evaluation results are shown in the table.

Examples 125 to 127

A memory circuit was formed in the same manner as in Examples 102 to 120 by the method described in Table 6. However, a solution in which tetraethyl ammonium tetrafluoroborate was used as the conductive auxiliary agent 2 in a saturated solution of the conductive auxiliary agent 1 and coexisted at a saturated concentration was used. The evaluation results are shown in the table.

Under the condition of the conductive auxiliary agent 2, even when the metal ion constituting the porous polymeric metal complex is a copper ion, the number of repetitions is excellent.

Examples 128 to 130

A memory circuit was formed in the same manner as in Examples 102 to 120 by the method described in Table 6. However, when synthesizing the porous polymeric metal complex, the conductive auxiliary agent 1 described in Table 6 coexisted at a concentration of 1/10 of the saturation concentration (easy bottle method). The evaluation results are shown in Table 8. When prepared by the easy bottle method, the porous polymer metal complex network has excellent memory retention time even in three dimensions.

Example 131

The copper plate was immersed in 50 ml of a trimesic acid ethanol solution having a concentration of 0.2 mM and allowed to react at 40 캜 for 6 hours. The copper plate was taken out of the solution as a tweezers, immersed in an anhydrous ethanol solution three times for 10 seconds, Followed by drying under reduced pressure at room temperature. As a result of the analysis of the powder X-ray, it was confirmed that it was a compound described as HKUST-1 in Williams et al., Science (1999) 283, 1148. A memory circuit was constructed in the same manner as in Example 101 by using this material.

Example 132

As in Example 131, however, a memory circuit was constructed using BEDT-TTF as the conductive auxiliary agent 1.

Example 133

As in Example 131, terephthalic acid was used instead of trimethic acid. Compounds formed on copper plates are described in Tannenbaum et al., Eur. J. Inorg. Chem. , 2009, 2338 (a porous high molecular metal complex represented by Cu (tpa). (Dmf) composed of Cu ^{2 +} ions, terephthalic acid and guest molecules of DMF). The memory circuit was constructed using this material.

Example 134

In the same manner as in Example 133, however, a memory circuit was constructed using BEDT-TTF as the conductive auxiliary agent 1.

Comparative Example 6

A memory circuit was constructed in the same manner as in Example 101. [ However, impregnation of the solution of the conductive auxiliary agent was not performed. This memory circuit did not exhibit the memory effect.

Comparative Example 7

A memory circuit was constructed in the same manner as in Example 101. [ However, no active metal was used and platinum was used for both electrodes. This memory circuit did not exhibit the memory effect.

Comparative Example 8

A memory circuit was constructed in the same manner as in Example 101 by preparing a material according to the document described in Table 7. [ That is, Bi (group 15) was used as the metal ion. This memory circuit did not exhibit the memory effect.

The present invention can provide a novel porous polymer metal complex conductor obtained by adding a conductive auxiliary agent to a porous polymer metal complex and a microswitch composed of two kinds of electrode metals. The porous polymer metal complex conductor of the present invention and the microswitch formed of two kinds of metals can be used as a memory. The present invention can also be applied to a random access memory, a storage class memory and an integrated circuit (memory chip, LSI), a storage device (SSD, SD card, USB memory, etc.) ) Circuit switching switches, and other devices (sensors).

Claims (21)

A first electrode, a second electrode, and a porous polymer metal complex conductor,
Wherein the porous polymer metal complex conductor is represented by the following formula (1)
Wherein the metal constituting the first electrode and the metal constituting the second electrode have different redox potentials.
[ML_x]_n(D)_y (One)
Wherein M represents a metal ion selected from Groups 2 to 13 of the Periodic Table of the Elements and L represents a ligand capable of forming two or more functional groups capable of coordinating to M and capable of crosslinking with two of M , And D represents a conductive auxiliary agent not containing a metal element. x is from 0.5 to 4, and y is from 0.0001 to 20 per x. n is [ML_x], And n is 5 or more. The micro switch according to claim 1, wherein D is a compound having a carbon-carbon multiple bond in the molecule and containing a sulfur or nitrogen atom. The compound according to claim 1, wherein D is a compound having a carbon-carbon multiple bond in the molecule and having an electron-withdrawing group or an electron-donating group bonded to the carbon-carbon multiple bond, or an aromatic compound having a conjugated system developed, Smile switch. 4. The micro switch according to claim 2 or 3, wherein D is an acceptor compound selected from the group consisting of tetracyanoethylene, tetracyanoquinodimethane, benzoquinone, and derivatives thereof. 4. The micro switch according to claim 2 or 3, wherein D is a donor compound selected from tetrathiafulvalene or derivatives thereof. The micro switch according to any one of claims 1 to 5, wherein the porous polymer metal complex conductor contains two or more of the above-mentioned D's. The micro switch according to claim 6, wherein at least one of the two or more species D is an organic conductive auxiliary agent comprising an organic substance having a charge in a molecule. The micro switch according to claim 7, wherein the organic conductive auxiliary agent is selected from the group consisting of a quaternary ammonium salt, a phosphonium salt, an amine-alkali metal ion complex, an imidazolium salt, a pyridinium salt, and a sulfonium salt. The micro switch according to any one of claims 1 to 8, wherein the content of D is 0.001 to 30 mass% with respect to the porous polymer metal complex conductor. 10. The composition according to any one of claims 1 to 9, wherein M is a divalent, trivalent or tetravalent metal ion selected from chromium, manganese, iron, cobalt, nickel, copper, zinc, rare earth, zirconium, switch. 10. The micro switch according to any one of claims 1 to 9, wherein L is an aromatic compound containing two or more carboxyl groups in the molecule. 10. The micro switch according to any one of claims 1 to 9, wherein L is a non-aromatic compound containing two or more carboxyl groups in the molecule. 12. The micro switch according to claim 11, wherein L is an aromatic compound containing two or more nitrogen atoms of a satellites in a molecule. 13. The micro switch according to claim 12, wherein L is a non-aromatic compound containing two or more nitrogen atoms of a satellites in a molecule. 10. The method according to any one of claims 1 to 9, wherein M is at least one element selected from the group consisting of magnesium, aluminum, calcium, scandium, manganese, iron, iron, cobalt, nickel, copper, zinc, zirconium ruthenium, rhodium, Palladium, silver, cadmium, indium and rhenium,
Wherein L is a substituted or unsubstituted terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 2.7-naphthalene dicarboxylic acid, 4.4'-biphenyldicarboxylic acid, 4'-bipyridine, 1,4- (4-pyridyl) benzene, and substituted or unsubstituted imidazole. 16. The micro switch according to any one of claims 1 to 15, wherein the difference between the redox potential of the metal constituting the first electrode and the metal constituting the second electrode is 0 eV to 5.0 eV. 17. The method according to any one of claims 1 to 16, wherein the metal constituting the first electrode is a metal selected from the group consisting of Au, Pt, W, Ru, In, Rh,
Wherein the metal constituting the second electrode is a metal selected from the group consisting of Cu, Ag, Zn, Co, Mn and Al. _{A: (Tin-doped In 2 O} 3 ITO), doped with Nb titanium oxide, Ga or zinc oxide, and Nb doped with Al of claim 17 wherein the metal is, indium tin oxide constituting the first electrode in the Doped SrTiO ₃ , SrRuO ₃ , RuO _2, or IrO ₂ . An electronic device configured by using the micro switch according to any one of claims 1 to 18. A step of mixing a metal ion and a ligand to form a porous polymer metal complex,
Contacting the porous polymeric metal complex with the first and second electrodes,
A step of mixing the porous polymer metal complex brought into contact with the first and second electrodes and a conductive auxiliary agent to form a porous polymer metal complex conductor
A method of manufacturing a micro switch for a CB-RAM,
The metal ion is selected from Groups 2 to 13 of the periodic table,
The ligand is capable of containing two or more functional groups capable of coordinating with the metal ion within the structure and capable of crosslinking with two of the metal ions,
The conductive auxiliary agent is a material not containing a metal element,
Wherein the redox potential is different between a metal constituting the first electrode and a metal constituting the second electrode. A step of mixing a metal ion, a ligand, and a conductive auxiliary agent to form a porous polymer metal complex conductor,
A step of bringing the porous polymer metal complex conductor into contact with the first and second electrodes
And a second step of forming a micro switch,
The metal ion is selected from Groups 2 to 13 of the periodic table,
The ligand is capable of containing two or more functional groups capable of coordinating with the metal ion within the structure and capable of crosslinking with two of the metal ions,
The conductive auxiliary agent is a material not containing a metal element,
Wherein a redox potential is different between a metal constituting the first electrode and a metal constituting the second electrode.

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